CN109806774A - A kind of thin layer composite film support and preparation method thereof and utilized thin film composite membranes - Google Patents
A kind of thin layer composite film support and preparation method thereof and utilized thin film composite membranes Download PDFInfo
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Abstract
The invention belongs to field of membrane material more particularly to a kind of thin layer composite film support and preparation method thereof and utilized thin film composite membranes.Thin layer composite film support provided by the invention includes top porous support layer and bottom porous support unit；Each layer of porous support layer in top porous support layer and bottom porous support unit is made of casting solution；Top porous support layer is different from the casting solution component that at least one layer of porous support layer in bottom porous support unit uses in the preparation.Thin layer composite film support provided by the invention includes at least two layers of supporting layer, formula of casting by regulating and controlling to prepare different supporting layers can carry out the property of respective support layer separately adjustable, to make the surface nature of supporter be more suitable for combining active separating layer, and other layers can provide higher mechanical strength then for supporter.Therefore, the utilized thin film composite membranes prepared on the Multi-layer supporting body through interfacial polymerization method can have more excellent comprehensive performance.
Description
Technical field
The invention belongs to field of membrane material more particularly to a kind of thin layer composite film support and preparation method thereof and thin layer are multiple
Close film.
Background technique
Liquid filtering is carried out using utilized thin film composite membranes and separation has been widely used in water process, blood purification, organic
The fields such as solvent refining.The utilized thin film composite membranes such as especially reverse osmosis, nanofiltration, filtering accuracy can reach sub-nanometer rank.Preparation
High performance utilized thin film composite membranes are always the hot spot direction in international membrane technology research and development field.Utilized thin film composite membranes are usually by being located at bottom
Porous supporting body and one layer or it is several layers of be compounded on supporter active separating layer composition.Currently, utilized thin film composite membranes are in reverse osmosis
Permeable membrane and nanofiltration membrane field are most widely used.
For utilized thin film composite membranes, the property of supporter has vital influence to the performance of gained composite membrane.Branch
The surface nature of support body is directly related between active separating layer and supporter and is firmly combined degree, the desalination to gained composite membrane
Rate, water flux, chlorine-resistant oxidisability have a major impact.The inside solid degree of supporter has weight to the pressure-resistant property of gained composite membrane
It influences.In order to adjust these influences, the better composite membrane of performance is obtained, technical staff does a lot of work.Such as pass through change
The preparation process of supporting layer, type and concentration, the type and content of additive, the type of solvent including changing film polymer
With content, the hydrophily of supporter etc..But the supporter that these methods obtain is often film surface porosity and film internal holes
Synchronized relation is presented in gap rate, i.e., surface porosity factor is high, then interior porosity is also high, and surface porosity factor is low, then interior porosity
It is low.And the film of high voltage, high throughput and equipment with high desalinization is had both for preparation, then it needs to realize the inside of supporter and surface
Asynchronous adjusting.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of thin layer composite film support and preparation method thereof and thin layer are multiple
Close film, supporter provided by the invention can real surface and internal physical and chemical performance it is separately adjustable, through boundary on the supporter
The utilized thin film composite membranes of face polymerization preparation have excellent resistance to pressure, salt rejection rate, water flux and service life.
The present invention provides a kind of thin layer composite film supports, including the top porous support layer being in contact and bottom porous
Support unit, the bottom porous support unit are made of at least one layer of porous support layer；
Each layer porous support layer in the top porous support layer and bottom porous support unit is by casting film
Liquid is made；
The top porous support layer is being prepared at least one layer of porous support layer in the bottom porous support unit
When the casting solution component that uses it is different.
Preferably, porosity≤99% of the top porous support layer；
Average pore size≤500nm of the top porous support layer；
The top porous support layer with a thickness of 1~100 μm.
Preferably, in the bottom porous support unit each layer of porous support layer porosity≤99%；
Average pore size≤500nm of each layer of porous support layer in the bottom porous support unit；
Each layer of porous support layer with a thickness of 1~100 μm in the bottom porous support unit.
Preferably, the casting solution includes polymer and solvent；
The polymer includes in polysulfones, polyether sulfone, polyacrylonitrile, polyimides, Kynoar and polyvinyl chloride
It is one or more；
The solvent includes dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, trichlorine
One of methane and glycol monoethyl ether are a variety of.
It preferably, further include additive in the casting solution；
The additive include polyethylene glycol, polyvinylpyrrolidone, ethylene glycol monomethyl ether, water, tributyl phosphate, glycerol,
One of triethylene glycol and surfactant are a variety of.
The present invention provides a kind of preparation methods of thin layer composite film support described in above-mentioned technical proposal, including following step
It is rapid:
A) nascent liquid film is provided, the nascent liquid film includes the nascent liquid film list of the nascent liquid film layer in top and bottom being in contact
Member, the nascent liquid film unit in the bottom are made of the nascent liquid film layer of at least one layer；
Each layer nascent liquid film layer in the nascent liquid film unit of the nascent liquid film layer in the top and bottom is by casting film
Liquid is formed after film；
The nascent liquid film layer in the top is being prepared with the nascent liquid film layer of at least one layer in the nascent liquid film unit in the bottom
When the casting solution component that uses it is different；
B) the nascent liquid film is subjected to gelation, washs later, obtains thin layer composite film support.
Preferably, the nascent liquid film is prepared in accordance with the following methods:
A1) more parts of casting solutions are carried out to multi-layer co-extruded, the nascent liquid film of formation at film base material；
Or,
A2) the successively coating multiple casting solution at film base material forms nascent liquid film.
Preferably, in step b), temperature≤100 DEG C of the gelation；The time of the gelation≤5min.
Preferably, in step b), the temperature of the washing is 0~100 DEG C；The time of the washing≤10min.
The present invention provides a kind of utilized thin film composite membranes, including thin layer composite film support described in above-mentioned technical proposal and again
Close the active separating layer in the top porous support layer surface.
Compared with prior art, the present invention provides a kind of thin layer composite film support and preparation method thereof and thin layer composites
Film.Thin layer composite film support provided by the invention includes the top porous support layer and bottom porous support unit being in contact,
The bottom porous support unit is made of at least one layer of porous support layer；The top porous support layer and bottom porous support
Each layer porous support layer in unit is made of casting solution；The top porous support layer and the bottom porous branch
The casting solution component that at least one layer of porous support layer in support unit uses in the preparation is different.Thin layer composite provided by the invention
Film support includes at least two layers of supporting layer, and the formula of casting by regulating and controlling to prepare different supporting layers can be to respective support layer
Property carry out separately adjustable, so that the surface nature of supporter be made to be more suitable for combining active separating layer, and other layers then can be
Supporter provides higher mechanical strength.Therefore, the utilized thin film composite membranes prepared on the Multi-layer supporting body through interfacial polymerization method
There can be more excellent comprehensive performance: such as better resistance to pressure, higher salt rejection rate and water flux, longer service life
Deng.The results showed that water flux >=27L.m of utilized thin film composite membranes made of supporter provided by the present invention-2.h-1, desalination
Rate >=99%, stress levels >=12MPa.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the thin layer composite film support preparation technology flow chart that the embodiment of the present invention 1 provides；
Fig. 2 is the thin layer composite film support preparation technology flow chart that the embodiment of the present invention 2 provides；
Fig. 3 is that the embodiment of the present invention 11 provides test device schematic diagram.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of thin layer composite film supports, including the top porous support layer being in contact and bottom porous
Support unit, the bottom porous support unit are made of at least one layer of porous support layer；
Each layer porous support layer in the top porous support layer and bottom porous support unit is by casting film
Liquid is made；
The top porous support layer is being prepared at least one layer of porous support layer in the bottom porous support unit
When the casting solution component that uses it is different.
Thin layer composite film support provided by the invention includes the top porous support layer being in contact and bottom porous support
Unit, the bottom porous support unit are made of at least one layer of porous support layer, preferably include 1~10 layer, and concretely 1
Layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers or 10 layers.In the present invention, the top porous support layer and bottom
Each layer porous support layer in open support unit is made after film, gelation and washing of casting solution.Its
In, the casting solution includes polymer and solvent；The polymer includes but is not limited to polysulfones (PSF), polyether sulfone (PES), gathers
One of acrylonitrile (PAN), polyimides (PI), Kynoar (PVDF) and polyvinyl chloride (PVC) are a variety of；It is described poly-
The degree of polymerization for closing object is preferably 10~500, concretely 10,20,30,40,50,60,70,80,90,100,110,120,130,
140,150,160,170,180,190,200,250,300,350,400,450 or 500；The polymer containing in casting solution
Amount be preferably 5~90wt%, concretely 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%,
40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or
90wt%；The solvent includes but is not limited to dimethylformamide (DMF), dimethyl acetamide (DMAC), N- crassitude
One of ketone (NMP), dimethyl sulfoxide (DMSO), chloroform and glycol monoethyl ether (EGM) are a variety of.In the present invention
In, it is also preferable to include additive in the casting solution, the additive includes but is not limited to polyethylene glycol (PEG), polyethylene pyrrole
One of pyrrolidone (PVP), ethylene glycol monomethyl ether, water, tributyl phosphate, glycerol, triethylene glycol and surfactant are a variety of；Institute
The number-average molecular weight for stating polyethylene glycol is preferably 100~100000, and concretely 100,1000,10000 or 100000；It is described poly-
The number-average molecular weight of vinylpyrrolidone is preferably 100~100000, and concretely 100,1000,10000 or 100000；It is described
Surfactant includes but is not limited to glycidol ether；Content of the additive in casting solution is preferably 5~90wt%, tool
Body can for 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%,
55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt%.In the present invention, the top
The casting solution group that at least one layer of porous support layer in porous support layer and the bottom porous support unit uses in the preparation
Divide difference.In the present invention, by adjusting the component of casting solution, different physical and chemical performances, especially different porosities can be obtained
Porous support layer.
In the present invention, the porosity of the top porous support layer preferably≤99%, concretely 5%, 10%,
15%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%,
34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%,
49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%,
64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%,
79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%,
94%, 95%, 96%, 97%, 98% or 99%；The average pore size of the top porous support layer preferably≤500nm, 1nm,
2nm、3nm、4nm、5nm、6nm、7nm、8nm、9nm、10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、
19nm、20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm、29nm、30nm、50nm、100nm、150nm、
200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm；The thickness of the top porous support layer is preferably 1~
100 μm, concretely 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15
μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μ
m、31μm、32μm、33μm、34μm、35μm、36μm、37μm、38μm、39μm、40μm、41μm、42μm、43μm、44μm、45μm、
46 μm, 47 μm, 48 μm, 49 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100 μm.
In the present invention, in the bottom porous support unit porosity of each layer of porous support layer independently preferably≤
99%, concretely 5%, 10%, 15%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%,
30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%,
45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%,
60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%,
75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%,
90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99%；It is each in the bottom porous support unit
Layer porous support layer average pore size independently preferably≤500nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm,
17nm、18nm、19nm、20nm、21nm、22nm、23nm、24nm、25nm、26nm、27nm、28nm、29nm、30nm、31nm、
32nm、33nm、34nm、35nm、36nm、37nm、38nm、39nm、40nm、41nm、42nm、43nm、44nm、45nm、46nm、
47nm, 48nm, 49nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm；Institute
The thickness for stating each layer of porous support layer in bottom porous support unit is independently preferably 1~100 μm, concretely 1 μm, 2 μ
m、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19
μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34μ
m、35μm、36μm、37μm、38μm、39μm、40μm、41μm、42μm、43μm、44μm、45μm、46μm、47μm、48μm、49μm、
50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100 μm；The bottom porous support unit
Overall thickness be preferably 10~120 μm, concretely 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm,
19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34
μm、35μm、36μm、37μm、38μm、39μm、40μm、41μm、42μm、43μm、44μm、45μm、46μm、47μm、48μm、49μ
M, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm or
120μm。
Thin layer composite film support provided by the invention includes at least two layers of supporting layer, prepares different supporting layers by regulation
Formula of casting can to the property of respective support layer carry out it is separately adjustable, so that the surface nature of supporter be made to be more suitable for tying
Active separating layer is closed, and other layers can provide higher mechanical strength then for supporter.Therefore, through boundary on the Multi-layer supporting body
The utilized thin film composite membranes of face polymerization preparation can have more excellent comprehensive performance: such as better resistance to pressure, higher de-
Salt rate and water flux, longer service life etc..The results showed that thin layer composite made of supporter provided by the present invention
Water flux >=27L.m of film-2.h-1, salt rejection rate >=99%, stress levels >=12MPa.
The present invention also provides a kind of preparation method of thin layer composite film support described in above-mentioned technical proposal, including it is following
Step:
A) nascent liquid film is provided, the nascent liquid film includes the nascent liquid film list of the nascent liquid film layer in top and bottom being in contact
Member, the nascent liquid film unit in the bottom are made of the nascent liquid film layer of at least one layer；
Each layer nascent liquid film layer in the nascent liquid film unit of the nascent liquid film layer in the top and bottom is by casting film
Liquid is formed after film；
The nascent liquid film layer in the top is being prepared with the nascent liquid film layer of at least one layer in the nascent liquid film unit in the bottom
When the casting solution component that uses it is different；
B) the nascent liquid film is subjected to gelation, washs later, obtains thin layer composite film support.
In preparation method provided by the invention, nascent liquid film is provided first, the nascent liquid film includes the top being in contact
The nascent liquid film unit of the nascent liquid film layer in portion and bottom, the nascent liquid film unit in the bottom are made of the nascent liquid film layer of at least one layer；
Each layer nascent liquid film layer in the nascent liquid film unit of the nascent liquid film layer in the top and bottom is by casting solution through film
After formed；At least one layer in the nascent liquid film unit of the nascent liquid film layer in the top and the bottom comes into being liquid film layer in the preparation
The casting solution component used is different.In the present invention, the composition of the casting solution hereinbefore by the agency of, it is no longer superfluous herein
It states.In the present invention, the number of plies of the nascent liquid film unit in bottom is preferably 1~10 layer in the nascent liquid film, concretely 1 layer, 2
Layer, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers or 10 layers；The overall thickness of the nascent liquid film is preferably 100~500 μm, tool
Body can be 100 μm, 120 μm, 150 μm, 170 μm, 200 μm, 230 μm, 250 μm, 270 μm, 300 μm, 320 μm, 350 μm, 370 μ
M, 400 μm, 420 μm, 450 μm, 470 μm or 500 μm；In the nascent liquid film top come into being liquid film layer thickness be preferably 10~
50 μm, concretely 10 μm, 12 μm, 15 μm, 17 μm, 20 μm, 23 μm, 25 μm, 27 μm, 30 μm, 32 μm, 35 μm, 37 μm, 40 μ
M, 42 μm, 45 μm, 47 μm or 50 μm.
In the present invention, the nascent liquid film can be prepared in accordance with the following methods:
A1) more parts of casting solutions carry out multi-layer co-extruded at film base material, form nascent liquid film；
Or,
A2) the successively coating multiple casting solution at film base material forms nascent liquid film.
In above-mentioned nascent liquid film preparation method provided by the invention, used at film base material is preferably non-woven fabrics.This
Described multi-layer co-extruded and coating concrete technology conditional parameter and device therefor is not particularly limited in invention, art technology
Personnel select suitable technological parameter and equipment according to the structure and thickness of prepared nascent liquid film.
In the present invention, after obtaining nascent liquid film, the nascent liquid film is subjected to gelation.Wherein, the gelation is excellent
It is selected in coagulating bath and carries out, the coagulating bath includes water, and it is also preferable to include organic solvent, the organic solvent includes but is not limited to
In dimethylformamide (DMF), dimethyl acetamide (DMAC), N-Methyl pyrrolidone (NMP) and dimethyl sulfoxide (DMSO)
It is one or more；Volume content of the organic solvent in coagulating bath is preferably 0.5~5%, concretely 0.5%,
1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.In the present invention, the temperature of the gelation is preferred
≤ 100 DEG C, concretely 0 DEG C, 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 9 DEG C, 10 DEG C, 11 DEG C, 12 DEG C, 13 DEG C,
14℃、15℃、16℃、17℃、18℃、19℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65
DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C；The time of the gelation is preferably≤5min, concretely
0.5min, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min.After gelation, obtain
To gel mould.
In the present invention, after obtaining gel mould, the gel mould is washed.Wherein, the washing is preferably solidifying
It is carried out in bath, the component of the coagulating bath hereinbefore by the agency of, details are not described herein.In the present invention, the washing
Temperature is preferably 0~100 DEG C, concretely 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50
DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C；Time of the washing preferably≤
10min, concretely 0.5min, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min,
5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min or 10min.Provided by the invention
In one embodiment, the gel mould is preferably successively washed in the coagulating bath of temperature increment, concretely: first 40~
2~3min is washed in 50 DEG C of coagulating bath, 2~3min is then washed in 55~60 DEG C of coagulating bath, finally at 65~70 DEG C
Coagulating bath in wash 1~2min.After washing, thin layer composite film support provided by the invention is obtained.
Preparation method provided by the invention prepares the formula of casting of different supporting layers by regulation, can be to respective support layer
Property carry out it is separately adjustable, so that the surface nature of the supporter of preparation be made to be more suitable for combining active separating layer, and other layers
Higher mechanical strength can be then provided for supporter.Therefore, through interfacial polymerization method on the Multi-layer supporting body of this method preparation
The utilized thin film composite membranes of preparation can have more excellent comprehensive performance: as better resistance to pressure, higher salt rejection rate and water are logical
Amount, longer service life etc..The results showed that utilized thin film composite membranes made of supporter using the method for the present invention preparation
Water flux >=27L.m-2.h-1, salt rejection rate >=99%, stress levels >=12MPa.
The present invention also provides a kind of utilized thin film composite membranes, including thin layer composite film support described in above-mentioned technical proposal and
It is compounded in the active separating layer of the top porous support layer surface of the thin layer composite film support.
Utilized thin film composite membranes provided by the invention include the thin layer composite film support and active separating layer, the activity point
Absciss layer is compounded in the top porous support layer surface of the thin layer composite film support, is existed by activated monomer by interfacial polymerization
The surface construction of the top porous support layer is formed.In the present invention, the activated monomer preferably includes aqueous phase monomers and has
Machine Xiang Danti, the aqueous phase monomers are preferably polyamine, including but not limited to m-phenylene diamine (MPD) (MPDA), p-phenylenediamine (PDDA),
One of o-phenylenediamine (OPDA) and equal benzene triamine are a variety of；The organic phase monomer is preferably polynary acyl chlorides, including but not
It is limited to pyromellitic trimethylsilyl chloride (TMC), o-phthaloyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, three acyl chlorides of 1,3,5- hexamethylene
With one of 1,3- chlorobenzoyl chloride -5- sulfuryl chlorio benzene or a variety of.
In the present invention, the utilized thin film composite membranes can be reverse osmosis membrane, nanofiltration membrane, forward osmosis membrane or gas thin layer composite
Film.
In the present invention, the utilized thin film composite membranes can be prepared in accordance with the following methods:
I) dry in the solution of utilized thin film composite membranes supporting body surface dipping aqueous phase monomers；
Ii the solution that organic phase monomer) is impregnated on the top porous support layer of the supporter by step i) processing, does
It is dry；
Iii) will pass through step ii) processing supporter washed and dried, obtain utilized thin film composite membranes.
In above-mentioned thin layer composite membrane preparation method provided by the invention, in step i), the solution of the aqueous phase monomers by
Aqueous phase monomers and water composition, content of the aqueous phase monomers in the solution is preferably 0.5~10wt%, concretely
0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%,
5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt% or 10wt%；Step
I) in, the thin layer composite film support is preferably immersed in the solution of aqueous phase monomers by the mode of the dipping, the leaching
The time of bubble is preferably 0.5~2min, concretely 0.5min, 0.6min, 0.7min, 0.8min, 0.9min, 1min,
1.1min, 1.2min, 1.3min, 1.4min, 1.5min, 1.6min, 1.7min, 1.8min, 1.9min or 2min；Step i)
In, the mode of the drying is preferably dried, and the time dried is preferably 0.5~2min, concretely 0.5min,
0.6min、0.7min、0.8min、0.9min、1min、1.1min、1.2min、1.3min、1.4min、1.5min、1.6min、
1.7min, 1.8min, 1.9min or 2min.
In above-mentioned thin layer composite membrane preparation method provided by the invention, step ii) in, the solution of the organic phase monomer
It is made of organic phase monomer and organic solvent, the organic solvent includes but is not limited to ISOPAR solvent, hexamethylene and ethyl ring
One of hexane is a variety of, and content of the organic phase monomer in the solution is preferably 0.05~1wt%, concretely
0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%,
0.5wt%, 0.55wt%, 0.6wt%, 0.65wt%, 0.7wt%, 0.75wt%, 0.8wt%, 0.85wt%, 0.9wt%,
0.95wt% or 1wt%；Step ii) in, the mode of the dipping is preferably at the top of the supporter by step i) processing
Porous support layer goes up the solution of organic phase monomer；Step ii) in, the time of the dipping is preferably 10~150s, specifically may be used
For 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s or 150s；Step ii)
In, the mode of the drying is preferably dried, and the temperature of the drying is preferably 80~120 DEG C, concretely 80 DEG C, 85 DEG C,
90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C；The time of the drying is preferably 1~5min, concretely
1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min.
In above-mentioned thin layer composite membrane preparation method provided by the invention, step iii) in, the mode of the washing is preferred
It is washed successively to carry out alkali cleaning, primary washing, pickling, secondary washing and alcohol.Wherein, the reagent of the alkali cleaning includes but is not limited to carbon
Acid sodium aqueous solution, the concentration of the aqueous sodium carbonate are preferably 0.5~2wt%, concretely 0.5wt%, 0.6wt%,
0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%,
1.6wt%, 1.7wt%, 1.8wt%, 1.9wt% or 2wt%；The temperature of the alkali cleaning is preferably 20~40 DEG C, concretely
20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C or 40 DEG C；The time of the alkali cleaning is preferably 1~3min, concretely 1min, 1.5min,
2min, 2.5min or 3min.In the present invention, the temperature once washed is preferably 70~90 DEG C, concretely 70 DEG C, 75
DEG C, 80 DEG C, 85 DEG C or 90 DEG C；The time once washed is preferably 5~20min, concretely 5min, 10min, 15min
Or 20min.In the present invention, the reagent of the pickling includes but is not limited to aqueous citric acid solution, the aqueous citric acid solution
Concentration is preferably 2~5wt%, concretely 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt%；
The temperature of the pickling is preferably 70~90 DEG C, concretely 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；The time of the pickling
Preferably 1~3min, concretely 1min, 1.5min, 2min, 2.5min or 3min.In the present invention, the secondary washing
Temperature is preferably 70~90 DEG C, concretely 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；The time of the secondary washing is preferably
5~20min, concretely 5min, 10min, 15min or 20min.In the present invention, the reagent that the alcohol is washed includes but unlimited
In glycerine water solution, the concentration of the glycerine water solution is preferably 10~30wt%, and concretely 10,15,20,25 or 30；Institute
Stating the time that alcohol is washed is preferably 0.5~2min, concretely 0.5min, 1min, 1.5min or 2min.
In above-mentioned thin layer composite membrane preparation method provided by the invention, step iii) in, the mode of the drying is preferred
For drying, the temperature of the drying is preferably 70~110 DEG C, concretely 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C,
100℃,105℃,110℃；The drying time is preferably 2~10min, concretely 2min, 3min, 4min, 5min,
6min, 7min, 8min, 9min or 10min.
Utilized thin film composite membranes provided by the invention are prepared using supporter provided by the invention, therefore are had more excellent
Comprehensive performance: such as better resistance to pressure, higher salt rejection rate and water flux, longer service life.The results showed that
Water flux >=27L.m of utilized thin film composite membranes provided by the invention-2.h-1, salt rejection rate >=99%, stress levels >=12MPa.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
In following embodiments of the invention, the degree of polymerization of each polymer in casting solution is 150.
Embodiment 1
1) preparation of Multi-layer supporting body:
The supporter being made of two layers of polymers film layer is prepared using Double-layered slit extrusion die, by coextrusion processes,
Its process flow is as shown in Figure 1, Fig. 1 is the thin layer composite film support preparation technology flow chart that the embodiment of the present invention 1 provides.The
The preparation process condition of one layer (that is, bottom) are as follows: casting solution group becomes PSF (20wt%), NMP (75wt%), PEG (5wt%),
160 μm of liquid layer thickness are squeezed out, liquid layer rate of extrusion is 10 ms/min；The preparation process condition of the second layer (that is, top layer) are as follows: casting
The group of film liquid becomes PSF (40wt%), NMP (50wt%), PEG (10wt%), squeezes out 40 μm of liquid layer thickness, liquid layer rate of extrusion
It is 10 ms/min.Two layers of nascent liquid layer was stacked on the non-woven fabrics for being expressed into synchronous operation, by about 3 seconds time intervals
Air section operation, the non-woven fabrics for carrying film layer is immersed in coagulating bath, coagulating bath by 98% volume ratio water and 2% volume ratio
NMP composition, temperature control at 20 DEG C or less.After impregnating 1 minute in the coagulating bath, the film strips of generation are further in temperature
It rinses 2 minutes, is rinsed 2 minutes in the third coagulating bath that temperature is 55~60 DEG C, in temperature in 40~50 DEG C of the second gelation
Degree obtains Multi-layer supporting body to rinse 1 minute in 65~70 DEG C of the 4th coagulating bath.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 20 μm, porosity 85%, pore-size distribution be in 5~
70nm, average pore size 22nm；Top layer thickness is 10 μm, and porosity 63%, pore-size distribution is in 2~20nm, average pore size
For 10nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Comparative example 1
1) preparation of porous supporting body:
The casting solution that will be made of the n,N-Dimethylformamide (DMF) of the polysulfones of 20% (weight percent), 80%, benefit
With single layer knifing coating machine knifing on non-woven fabrics.Control knife gap is 260um, is immersed in water coagulating bath at room temperature and forms micropore
Supporting layer, polysulfone supporting layer obtained save stand-by in water.The porous support layer overall thickness of preparation is 45 μm, and porosity is
89%, pore-size distribution is in 5~75nm, average pore size 28nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 2
1) preparation of Multi-layer supporting body:
It is made of using a flat scraper and a slot extrusion dies group technology preparation two layers of polymers film layer
Supporter, process flow is as shown in Fig. 2, Fig. 2 is the thin layer composite film support preparation process stream that the embodiment of the present invention 2 provides
Cheng Tu.The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PSF (20wt%), NMP (75wt%), PEG
The casting solution is imported in the hopper of flat scraper configuration, the increasing of support membrane is done using the non-woven fabrics with a thickness of 90 μm by (5wt%)
Strong layer, the nonwoven thickness are 90 μm, spread over below scraper, and control scraper height is 250 μm, and control substrate travel speed is
10 ms/min；The preparation process condition of the second layer (that is, top layer) are as follows: the group of casting solution becomes PSF (40wt%), NMP
(50wt%), PEG (10wt%) squeeze out 40 μm of liquid layer thickness, this layer is expressed into the preceding layer in advancing, forms stacking knot
Structure, the rate of extrusion for controlling this layer of liquid layer is 10 ms/min.Air section operation by about 3 seconds time intervals, carries film layer
Non-woven fabrics immersed in coagulating bath, coagulating bath is made of the water of 98% volume ratio and the NMP of 2% volume ratio, temperature control exists
20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film strips of generation are further solidifying in second that temperature is 40~50 DEG C
Be to be rinsed 2 minutes in 55~60 DEG C of third coagulating bath in temperature Gu rinse 2 minutes in bath, temperature for 65~70 DEG C the
It is rinsed 1 minute in four coagulating baths, obtains Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 35 μm, porosity 83%, pore-size distribution be in 5~
70nm, average pore size 25nm；Top layer thickness is 10 μm, and porosity 63%, pore-size distribution is in 2~35nm, average pore size
For 16nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 3
1) preparation of Multi-layer supporting body:
It is made of using a comma scraper and a slot extrusion dies group technology preparation two layers of polymers film layer
Supporter.The preparation process condition of first layer (that is, bottom) are as follows: casting solution group become PSF (20wt%), NMP (75wt%),
The casting solution is imported in the hopper of comma scraper configuration, does support membrane using the non-woven fabrics with a thickness of 90 μm by PEG (5wt%)
Enhancement layer, which is 90 μm, spreads over below comma scraper, and control scraper height is 250 μm, controls substrate row
It is 10 ms/min into speed；The preparation process condition of the second layer (that is, top layer) are as follows: the group of casting solution becomes PSF (40wt%),
NMP (50wt%), PEG (10wt%) squeeze out 40 μm of liquid layer thickness, this layer is expressed into the preceding layer in advancing, forms heap
Pile structure, the rate of extrusion for controlling this layer of liquid layer is 10 ms/min.Air section operation by about 3 seconds time intervals, carries
The non-woven fabrics of film layer has immersed in coagulating bath, and coagulating bath is made of the water of 98% volume ratio and the NMP of 2% volume ratio, temperature control
System is at 20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film strips of generation are further in that temperature is 40~50 DEG C
Rinsed 2 minutes in two coagulating baths, temperature is rinse 2 minutes in 55~60 DEG C of third coagulating bath, temperature for 65~70 DEG C the
It is rinsed 1 minute in four coagulating baths, obtains Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 40 μm, porosity 80%, pore-size distribution be in 6~
65nm, average pore size 23nm；Top layer thickness is 10 μm, and porosity 60%, pore-size distribution is in 3~25nm, average pore size
For 10nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 4
1) preparation of Multi-layer supporting body:
The branch being made of three one polymer film layers is prepared using three layers of slit coextrusion die head, by coextrusion processes
Support layer.The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PSF (15wt%), NMP (80wt%), PEG
(5wt%) squeezes out 100 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min；The preparation process of the second layer (that is, middle layer)
Condition are as follows: casting solution group becomes PSF (20wt%), NMP (75wt%), PEG (5wt%), squeezes out 80 μm of liquid layer thickness, liquid layer squeezes
Rate is 10 ms/min out；The preparation process condition of third layer (that is, top layer) are as follows: the group of casting solution becomes PSF (40wt%),
NMP (50wt%), PEG (10wt%) squeeze out 20 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min.Three layers of nascent liquid layer
It is stacked on the non-woven fabrics for being expressed into synchronous operation, the air section by about 3 seconds time intervals is run, and carries the nothing of film layer
Woven fabric has immersed in coagulating bath, and coagulating bath is made of the water of 98% volume ratio and the NMP of 2% volume ratio, and temperature is controlled at 20 DEG C
Below.After impregnating certain 1 minute in the coagulating bath, the film strips of generation are further 40~50 DEG C of the second gelation in temperature
Middle rinsing 2 minutes, temperature is rinses 2 minutes in 55~60 DEG C of third coagulating bath, the 4th coagulating bath that temperature is 65~70 DEG C
Middle rinsing 1 minute, obtains Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment is 15 μm, and porosity 89%, pore-size distribution is in 10
~85nm, average pore size 39nm；Intermediate layer thickness is 15 μm, and porosity 65%, pore-size distribution is in 8~65nm, average
Aperture is 23nm；Top layer thickness is 8 μm, and porosity 28%, pore-size distribution is in 3~25nm, average pore size 10nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 5
1) preparation of Multi-layer supporting body:
The supporting layer being made of two layers of polymers film layer is prepared using Double-layered slit extrusion die, by coextrusion processes.
The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PSF (20wt%), DMAC (75wt%), PVP
(5wt%) squeezes out 160 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min；The preparation process item of the second layer (that is, top layer)
Part are as follows: the group of casting solution becomes PSF (40wt%), DMAC (50wt%), PEG (10wt%), squeezes out 40 μm of liquid layer thickness, liquid layer
Rate of extrusion is 10 ms/min.The nascent liquid layer of twenty percent is stacked on the non-woven fabrics for being expressed into synchronous operation, when by about 3 seconds
Between the air section operation that is spaced, the non-woven fabrics for carrying film layer immersed in coagulating bath, coagulating bath by 98% volume ratio water and
The DMAC of 2% volume ratio is formed, and temperature is controlled at 20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film strips of generation
It further rinses 2 minutes in the second gelation that temperature is 40~50 DEG C, is floated in the third coagulating bath that temperature is 55~60 DEG C
It washes 2 minutes, is rinsed 1 minute in the 4th coagulating bath that temperature is 65~70 DEG C, obtain Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 27 μm, porosity 78%, pore-size distribution be in 8~
65nm, average pore size 32nm；Top layer thickness is 16 μm, and porosity 62%, pore-size distribution is in 2~25nm, average pore size
For 11nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 6
1) preparation of Multi-layer supporting body:
The supporting layer being made of two layers of polymers film layer is prepared using Double-layered slit extrusion die, by coextrusion processes.
The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PSF (20wt%), DMF (70wt%), PEG
(10wt%) squeezes out 160 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min；The preparation process of the second layer (that is, top layer)
Condition are as follows: the group of casting solution becomes PSF (40wt%), DMF (50wt%), PEG (10wt%), squeezes out 40 μm of liquid layer thickness, liquid
Layer rate of extrusion is 10 ms/min.The nascent liquid layer of twenty percent was stacked on the non-woven fabrics for being expressed into synchronous operation, by about 3 seconds
The air section of time interval is run, and the non-woven fabrics for carrying film layer has immersed in coagulating bath, coagulating bath by 98% volume ratio water
It is formed with the DMF of 2% volume ratio, temperature is controlled at 20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film of generation
Band further rinses 2 minutes in the second gelation that temperature is 40~50 DEG C, in the third coagulating bath that temperature is 55~60 DEG C
Rinsing 2 minutes, temperature obtain Multi-layer supporting body to rinse 1 minute in 65~70 DEG C of the 4th coagulating bath.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 28 μm, porosity 82%, pore-size distribution be in 8~
65nm, average pore size 26nm；Top layer thickness is 16 μm, and porosity 56%, pore-size distribution is in 3~25nm, average pore size
For 10nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 7
1) preparation of Multi-layer supporting body:
The supporting layer being made of two layers of polymers film layer is prepared using Double-layered slit extrusion die, by coextrusion processes.
The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PES (25wt%), NMP (70wt%), PEG
(5wt%) squeezes out 160 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min；The preparation process item of the second layer (that is, top layer)
Part are as follows: the group of casting solution becomes PSF (40wt%), NMP (50wt%), PEG (10wt%), squeezes out 40 μm of liquid layer thickness, liquid layer
Rate of extrusion is 10 ms/min.The nascent liquid layer of twenty percent is stacked on the non-woven fabrics for being expressed into synchronous operation, when by about 3 seconds
Between the air section operation that is spaced, the non-woven fabrics for carrying film layer immersed in coagulating bath, coagulating bath by 98% volume ratio water and
The NMP of 2% volume ratio is formed, and temperature is controlled at 20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film strips of generation
It further rinses 2 minutes in the second gelation that temperature is 40~50 DEG C, is floated in the third coagulating bath that temperature is 55~60 DEG C
It washes 2 minutes, is rinsed 1 minute in the 4th coagulating bath that temperature is 65~70 DEG C, obtain Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 32 μm, porosity 69%, pore-size distribution be in 8~
55nm, average pore size 20nm；Top layer thickness is 12 μm, and porosity 53%, pore-size distribution is in 3~25nm, average pore size
For 10nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group as the m-phenylene diamine (MPD) of 2.0wt%, 1.0wt% triethylamine,
The water of 97wt%；Organic phase solution group is as three formyl chloride of isophthalic of 0.1wt%, the ISOPAR solvent of 99.9wt%；By step
1) the Multi-layer supporting body prepared, which was dipped into aqueous phase solution after 1 minute, takes out, is blown the remaining drop of film surface, then off with air knife
It dries in air 1 minute；In the top layer of supporter (that is, front), upper organic phase solution, control are single-side impregnated organic later
After phase solution 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 8
1) preparation of Multi-layer supporting body:
The supporting layer being made of two layers of polymers film layer is prepared using Double-layered slit extrusion die, by coextrusion processes.
The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PSF (20wt%), NMP (75wt%), PEG
(5wt%) squeezes out 160 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min；The preparation process item of the second layer (that is, top layer)
Part are as follows: the group of casting solution becomes PSF (40wt%), NMP (50wt%), PEG (10wt%), squeezes out 40 μm of liquid layer thickness, liquid layer
Rate of extrusion is 10 ms/min.The nascent liquid layer of twenty percent is stacked on the non-woven fabrics for being expressed into synchronous operation, when by about 3 seconds
Between the air section operation that is spaced, the non-woven fabrics for carrying film layer immersed in coagulating bath, coagulating bath by 98% volume ratio water and
The NMP of 2% volume ratio is formed, and temperature is controlled at 20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film strips of generation
It further rinses 2 minutes in the second gelation that temperature is 40~50 DEG C, is floated in the third coagulating bath that temperature is 55~60 DEG C
It washes 2 minutes, is rinsed 1 minute in the 4th coagulating bath that temperature is 65~70 DEG C, obtain Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 26 μm, porosity 85%, pore-size distribution be in 8~
65nm, average pore size 30nm；Top layer thickness is 15 μm, and porosity 59%, pore-size distribution is in 3~26nm, average pore size
For 11nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group becomes the piperazine of 1.0wt%, the sodium hydroxide of 1.0wt%, 98wt%
Water；Organic phase solution group is as three formyl chloride of isophthalic of 0.4wt%, the ISOPAR solvent of 99.6wt%；It prepared by step 1)
Multi-layer supporting body be dipped into aqueous phase solution after 1 minute and take out, with air knife blown off the remaining drop of film surface, then in air
In dry 1 minute；Organic phase solution is gone up in the top layer of supporter (that is, front) later, controls single-side impregnated organic phase solution
After 30 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes, takes out film
It is immersed in that temperature is 30 DEG C, concentration is 2 minutes in the aqueous sodium carbonate of 1.0wt%, being then dipped into temperature is 80 DEG C
Clear water in 10 minutes；It is immersed in that temperature is 80 DEG C, concentration is then to exist 2 minutes in the aqueous citric acid solution of 3.0wt% later
It is rinsed 10 minutes in the clear water that temperature is 80 DEG C.After gained film is impregnated 1 minute in the glycerine water solution that concentration is 20wt%,
It is dried in baking oven at a temperature of 90 °C after five minutes, obtains reverse osmosis composite membrane.
Embodiment 9
1) preparation of Multi-layer supporting body:
It is made of using a flat scraper and a slot extrusion dies group technology preparation two layers of polymers film layer
Supporter.The preparation process condition of first layer (that is, bottom) are as follows: casting solution group become PSF (20wt%), NMP (75wt%),
The casting solution is imported in the hopper of flat scraper configuration, does support membrane using the non-woven fabrics with a thickness of 90 μm by PEG (5wt%)
Enhancement layer, which is 90 μm, spreads over below scraper, and control scraper height is 250 μm, and control substrate is advanced speed
Degree is 10 ms/min；The preparation process condition of the second layer (that is, top layer) are as follows: the group of casting solution becomes PSF (40wt%), NMP
(50wt%), PEG (10wt%) squeeze out 40 μm of liquid layer thickness, this layer is expressed into the preceding layer in advancing, forms stacking knot
Structure, the rate of extrusion for controlling this layer of liquid layer is 10 ms/min.Air section operation by about 3 seconds time intervals, carries film layer
Non-woven fabrics immersed in coagulating bath, coagulating bath is made of the water of 98% volume ratio and the NMP of 2% volume ratio, temperature control exists
20 DEG C or less.After impregnating certain 1 minute in the coagulating bath, the film strips of generation are further solidifying in second that temperature is 40~50 DEG C
Gu rinse 2 minutes in bath, temperature is rinse 2 minutes in 55~60 DEG C of third coagulating bath, and temperature the 4th is coagulated for 65~70 DEG C
Gu rinsing 1 minute in bath, Multi-layer supporting body is obtained.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment be 11 μm, porosity 79%, pore-size distribution be in 8~
65nm, average pore size 23nm；Top layer thickness is 15 μm, and porosity 53%, pore-size distribution is in 2~25nm, average pore size
For 11nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group becomes the piperazine of 0.5wt%, the triethylamine of 1.0wt%, 98.5wt%
Water；Organic phase solution group is as three formyl chloride of isophthalic of 0.2wt%, the cyclohexyl alkane solvents of 99.8wt%；By step 1)
The Multi-layer supporting body of preparation, which was dipped into aqueous phase solution after 1 minute, to be taken out, blows the remaining drop of film surface off with air knife, then exists
It is dried in air 1 minute；Organic phase solution is gone up in the top layer of supporter (that is, front) later, controls single-side impregnated organic phase
After solution 120 seconds, extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes,
Taking-up film is immersed in, and temperature is 30 DEG C, concentration is then to be dipped into temperature 2 minutes in the aqueous sodium carbonate of 1.0wt%
It is 10 minutes in 80 DEG C of clear water；It is immersed in that temperature is 80 DEG C, concentration is 2 minutes in the aqueous citric acid solution of 3.0wt% later,
Then it is rinsed 10 minutes in the clear water that temperature is 80 DEG C.Gained film is impregnated 1 in the glycerine water solution that concentration is 20wt%
After minute, is dried in baking oven at a temperature of 90 °C after five minutes, obtain reverse osmosis composite membrane.
Embodiment 10
1) preparation of Multi-layer supporting body:
The branch being made of three one polymer film layers is prepared using three layers of slit coextrusion die head, by coextrusion processes
Support layer.The preparation process condition of first layer (that is, bottom) are as follows: casting solution group becomes PSF (15wt%), NMP (80wt%), PEG
(5wt%) squeezes out 100 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min；The preparation process of the second layer (that is, middle layer)
Condition are as follows: casting solution group becomes PSF (20wt%), NMP (75wt%), PEG (5wt%), squeezes out 80 μm of liquid layer thickness, liquid layer squeezes
Rate is 10 ms/min out；The preparation process condition of third layer (that is, top layer) are as follows: the group of casting solution becomes PSF (40wt%),
NMP (50wt%), PEG (10wt%) squeeze out 20 μm of liquid layer thickness, and liquid layer rate of extrusion is 10 ms/min.Three layers of nascent liquid layer
It is stacked on the non-woven fabrics for being expressed into synchronous operation, the air section by about 3 seconds time intervals is run, and carries the nothing of film layer
Woven fabric has immersed in coagulating bath, and coagulating bath is made of the water of 98% volume ratio and the NMP of 2% volume ratio, and temperature is controlled at 20 DEG C
Below.After impregnating certain 1 minute in the coagulating bath, the film strips of generation are further 40~50 DEG C of the second gelation in temperature
Middle rinsing 2 minutes, temperature is rinses 2 minutes in 55~60 DEG C of third coagulating bath, the 4th coagulating bath that temperature is 65~70 DEG C
Middle rinsing 1 minute, obtains Multi-layer supporting body.
The underlayer thickness of Multi-layer supporting body manufactured in the present embodiment is 12 μm, and porosity 90%, pore-size distribution is in 12
~76nm, average pore size 41nm；Intermediate layer thickness is 18 μm, and porosity 82%, pore-size distribution is in 8~62nm, average
Aperture is 25nm；Top layer thickness is 6 μm, and porosity 53%, pore-size distribution is in 3~25nm, average pore size 11nm.
2) preparation of utilized thin film composite membranes:
Using interfacial polymerization method, aqueous phase solution group is male, 94wt% as piperazine, the carbonic acid of 1.0wt% of 5.0wt%
Water；Organic phase solution group is as three formyl chloride of isophthalic of 0.5wt%, the hexamethylene of 99.5wt%；Multilayer prepared by step 1)
Supporter, which was dipped into aqueous phase solution after 1 minute, to be taken out, blows the remaining drop of film surface off with air knife, then dries in air
1 minute；Organic phase solution is gone up in the top layer of supporter (that is, front) later, controls single-side impregnated organic phase solution after 30 seconds,
Extra organic phase solution is outwelled, gained film is put into convection oven, 100 DEG C of temperature, drying 3 minutes, film is taken out and is soaked
Bubble is then dipped into the clear water that temperature is 80 DEG C 2 minutes in the aqueous sodium carbonate that temperature is 30 DEG C, concentration is 1.0wt%
In 10 minutes；It is immersed in that temperature is 80 DEG C, concentration is then to be in temperature 2 minutes in the aqueous citric acid solution of 3.0wt% later
It is rinsed 10 minutes in 80 DEG C of clear water.After gained film is impregnated 1 minute in the glycerine water solution that concentration is 20wt%, in temperature
To dry after five minutes in 90 DEG C of baking ovens, reverse osmosis composite membrane is obtained.
Embodiment 11
Water is carried out using the reverse osmosis composite membrane that test device as shown in Figure 3 prepares Examples 1 to 10 and comparative example 1
The test of flux, salt rejection rate and stress levels:
1) water flux and salt rejection rate
Water flux in certain time by the volume of the water of film by being calculated, formula are as follows:
In formula (I), V is by the volume of the water of film in the unit time, and A is the area of film, and t is the time.
Salt rejection rate is calculated by the conductivity of material liquid and penetrating fluid, formula are as follows:
In formula (II), λpFor the conductivity of penetrating fluid, λfFor the conductivity of material liquid.
The test condition of water flux and salt rejection rate are as follows: room temperature, the NaCl aqueous solution of 2000ppm, the operating pressure of 2.0MPa.
Before film properties test, film needs under the pressure of 2.0MPa, stablizes 4 hours with pure water.All membrane samples all take three
Parallel sample, each sample are surveyed twice, are then averaged.
2) stress levels
A constant pressure value (other test conditions are consistent with the test condition of water flux and salt rejection rate) is set, film is monitored
Salt rejection rate and water flux change with time, if salt rejection rate, which can tend towards stability and be remained above, to be equal in 12 hours
98.0%, water flux gradually tends towards stability and is no more than 50% compared to the starting flux range of decrease, then it is assumed that the film tested can be born
The pressure rating, the maximum pressure grade that the film measured can be born, the as stress levels of institute's test film.
Test result is as shown in table 1:
1 performance of composite antiosmosis membrane testing result of table
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of thin layer composite film support, described including the top porous support layer and bottom porous support unit being in contact
Bottom porous support unit is made of at least one layer of porous support layer；
Each layer porous support layer in the top porous support layer and bottom porous support unit is by casting solution system
At；
The top porous support layer makes in the preparation at least one layer of porous support layer in the bottom porous support unit
Casting solution component is different.
2. thin layer composite film support according to claim 1, which is characterized in that the hole of the top porous support layer
Rate≤99%；
Average pore size≤500nm of the top porous support layer；
The top porous support layer with a thickness of 1~100 μm.
3. thin layer composite film support according to claim 1, which is characterized in that every in the bottom porous support unit
Porosity≤99% of one layer of porous support layer；
Average pore size≤500nm of each layer of porous support layer in the bottom porous support unit；
Each layer of porous support layer with a thickness of 1~100 μm in the bottom porous support unit.
4. thin layer composite film support according to claim 1, which is characterized in that the casting solution includes polymer and molten
Agent；
The polymer includes one of polysulfones, polyether sulfone, polyacrylonitrile, polyimides, Kynoar and polyvinyl chloride
Or it is a variety of；
The solvent includes dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, chloroform
With one of glycol monoethyl ether or a variety of.
5. thin layer composite film support according to claim 1, which is characterized in that further include addition in the casting solution
Agent；
The additive includes polyethylene glycol, polyvinylpyrrolidone, ethylene glycol monomethyl ether, water, tributyl phosphate, glycerol, three sweet
One of pure and mild surfactant is a variety of.
6. the preparation method of thin layer composite film support described in a kind of claim 1, comprising the following steps:
A) nascent liquid film is provided, the nascent liquid film includes the nascent liquid film unit of the nascent liquid film layer in top and bottom being in contact,
The nascent liquid film unit in the bottom is made of the nascent liquid film layer of at least one layer；
Each layer nascent liquid film layer in the nascent liquid film unit of the nascent liquid film layer in the top and bottom is passed through by casting solution
It is formed after film；
The nascent liquid film layer in the top makes in the preparation with the nascent liquid film layer of at least one layer in the nascent liquid film unit in the bottom
Casting solution component is different；
B) the nascent liquid film is subjected to gelation, washs later, obtains thin layer composite film support.
7. preparation method according to claim 6, which is characterized in that the nascent liquid film is prepared into accordance with the following methods
It arrives:
A1) more parts of casting solutions are carried out to multi-layer co-extruded, the nascent liquid film of formation at film base material；
Or,
A2) the successively coating multiple casting solution at film base material forms nascent liquid film.
8. preparation method according to claim 6, which is characterized in that in step b), temperature≤100 of the gelation
℃；The time of the gelation≤5min.
9. preparation method according to claim 6, which is characterized in that in step b), the temperature of the washing is 0~100
℃；The time of the washing≤10min.
10. a kind of utilized thin film composite membranes, including the described in any item thin layer composite film supports of Claims 1 to 5 and it is compounded in institute
State the active separating layer of top porous support layer surface.
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